CN101578248B - 压电陶瓷及压电元件 - Google Patents
压电陶瓷及压电元件 Download PDFInfo
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Abstract
本发明提供压动态d33常数大,在200℃的高温下也能够使用,相对于室温的动态d33常数的200℃的动态d33常数的变化小的压电陶瓷及压电元件。其特征在于,铋层状化合物在将组成式表示为Bi4Ti3O12·β[(1-γ)MlTiO3·γM2M3O3]时,满足0.405≤β≤0.498、0≤γ≤0.3,并且,M1为选自Sr、Ba、Ca、(Bi0.5Na0.5)、(Bi0.5Li0.5)及(Bi0.5K0.5)中的至少一种,M2为选自Bi、Na、K及Li中的至少一种,M3为选自Fe及Nb中的至少一种,相对于所述铋层状化合物即主成分100质量份,以氧化物(MnO2、Fe2O3)换算的总量计,含有0.05~1质量份的选自Mn及Fe中的至少一种。
Description
技术领域
本发明涉及压电陶瓷及压电元件,例如,涉及适用于谐振器、超声波振动器、超声波马达、或加速度传感器、爆震传感器、及AE传感器等压电传感器等,尤其,作为利用了厚度纵向振动的正压电效应的压电传感器适合使用的压电陶瓷及压电元件。
背景技术
从以往开始,作为利用了压电陶瓷的制品,例如有压电传感器、过滤器、压电谐振器、超声波振动器、超声波马达等。压电传感器作为冲击传感器或加速度传感器、或车载用爆震传感器使用,尤其,近年来,为了汽车的发动机的燃料费提高及减少排气(HC、NOx),进行着对用于通过直接检测汽缸内的压力来实现自喷射器的燃料喷射时序的最佳化的压电传感器的研究。
以往,作为压电陶瓷,使用了压电性高,例如,压电d常数大的PZT(钛酸锆酸铅)系材料或PT(钛酸铅)系材料。但是,指出PZT或PZ系材料含有约60质量%的铅,因此,因酸性雨而引起铅的溶出,有导致环境污染的危险性。因此,对不含有铅的压电材料寄托了高的期望。
另外,PZT或PT系材料的居里温度Tc为约200~300℃,因此,从在200℃左右的高温下使用的情况下压电d常数变差这一点、相对于室温的压电d常数,200℃的压电d常数大幅度变化的这一点等来说,用途上受到限制。例如,作为压力传感器使用的情况下,由于经时变化,压电d常数变差时,输出电压在相同的压力下也变化,在相对于室温的压电d常数的200℃的压电d常数的变化大的情况下,压力和输出电压的关系不是线形,因此,难以由输出电压算出正确的压力。另外,为了在200℃的高温下也得到稳定的压力传感器特性,还探讨了使用硅酸镓镧(Langasite,ランガサイト)或水晶等单晶。但是,在单晶的情况下,压电d常数小,另外,在加工时容易产生屑,导致容易破裂的问题,进而,存在单晶的制造成本极高的问题。
因此,作为不含有铅的压电陶瓷,提出了以铋层状化合物为主体的材料(例如,专利文献1)。在该以铋层状化合物为主体的压电陶瓷中,居里温度为约400℃以上的居多,那样的压电陶瓷具有高的耐热性,可以作为在发动机室内等高温下暴露的环境下使用的传感器元件来应用。
【专利文献1】特开2002-167276号公报
然而,将专利文献1中记载的以铋层状化合物为主体的压电陶瓷暴露于约200℃的高温下的用途例如作为用于直接检测汽缸内的压力的压力传感器用压电元件来使用的情况下,虽然具有高的耐热性,但存在决定压力的检测灵敏度的动态d33常数的温度变化率大,在室温~200℃的温度范围中,压力检测的分辨能力降低,灵敏度变差的问题。
还有,在此的动态d33常数是指:使用向压电元件直接施加了负载时的输出电压的实测值,利用后述式测定的d33常数。以往,d33常数是使用谐振阻抗法来测定,但在该方法中,施加于压电元件的负荷小,因此,不能评价施加了实际负载时的动态特性。因此,由施加了实际负载时的压力和输出电荷的关系测定d33常数(=输出电荷/压力变化),将其作为d33常数。
作为具体的测定方法,首先,向压电元件施加200N的偏压,除了所述偏压之外,以三角波形施加了150N的压力。用充电评价相对于施加于压电元件的三角波的峰压力150N的输出电荷Q。由相对于施加压力150N的输出电荷Q的关系可知,动态d33常数成为d33=Q/150N(负载变化)。即,动态d33常数的单位为C(库伦)/N,是指向压电元件施加了负载时的动态状态下的压电d33常数。
还有,施加200N的偏压是为了使向压电元件的牵引力不向压力方向作用而得到稳定的输出特性。另外,将负载的变化设为150N是为了包括检测作为本发明的应用例的发动机的汽缸内的压力变化所需的范围。
发明内容
从而,本发明的目的在于提供耐热性优越,并且,相对于室温的动态d33常数的200℃的动态d33常数的变化小的压电陶瓷及压电元件。
本发明的压电陶瓷,其特征在于,所述压电陶瓷以铋层状化合物为主成分,铋层状化合物在将组成式表示为Bi4Ti3O12·β[(1-γ)M1TiO3·γM2M3O3]时,满足0.405≤β≤0.498、0≤γ≤0.3,并且,M1为选自Sr、Ba、Ca、(Bi0.5Na0.5)、(Bi0.5Li0.5)及(Bi0.5K0.5)中的至少一种,M2为选自Bi、Na、K及Li中的至少一种,M3为选自Fe及Nb中的至少一种,相对于所述铋层状化合物即主成分100质量份,以氧化物(MnO2、Fe2O3)换算的总量计,含有0.05~1质量份的选自Mn及Fe中的至少一种。
另外,优选0.405≤β≤0.495、0.1≤γ≤0.3。优选M2M3O3为选自BiFeO3、NaNbO3、KNbO3及LiNbO3中的至少一种。本发明的压电元件,其特征在于,具备:所述压电陶瓷、和在该压电陶瓷的两面分别形成的电极。
根据本发明的压电陶瓷可知,该压电陶瓷以铋层状化合物为主成分,铋层状化合物在将组成式表示为Bi4Ti3O12·β[(1-γ)M1TiO3·γM2M3O3]时,满足0.405≤β≤0.498、0≤γ≤0.3,并且,M1为选自Sr、Ba、Ca、(Bi0.5Na0.5)、(Bi0.5Li0.5)及(Bi0.5K0.5)中的至少一种,M为选自Bi、Na、K及Li中的至少一种,M3为选自Fe及Nb中的至少一种,相对于所述铋层状化合物即主成分100质量份,以氧化物(MnO2、Fe2O3)换算的总量计,含有0.05~1质量份的选自Mn及Fe中的至少一种,由此铋层状化合物中的钙钛矿结晶结构为正方晶格和斜方晶格混在的组成相边界MPB,因此,相对于室温的动态d33常数,200℃的动态d33常数的变化在±5%以内的情况下,温度稳定性优越。
进而,得到大的动态d33常数,具有高的居里温度点,因此,即使放置于200℃的高温下,动态d33常数的劣化也少,能够具有耐热性优越的特性。
另外,在0.405≤β≤0.495、0.1≤γ≤0.3的情况下,能够进一步提高动态d33常数,并且,最佳烧成温度范围扩大,因此,特性不均变少,能够实现高的成品率。
M2M3O3为选自BiFeO3、NaNbO3、KNbO3及LiNbO3中的至少一种,由此能够进一步提高动态d33常数,并且,最佳烧成温度范围扩大,因此,特性不均变少,能够实现高的成品率。
由此,显示作为在高温环境下使用的压力传感器用压电陶瓷有用的特性,能够使用于用于直接检测车的发动机的汽缸内的压力的压力传感器或SMD(Surface Mount Device、表面安装部件)对应的冲击传感器、或因在200℃的高温下也不能确认压电性变差而能够在高温下使用的不挥发的强电介质存储器元件等中。
进而,本发明的压电元件具备所述压电陶瓷、和在该压电陶瓷的两面分别形成的电极,由此,高温为止的温度稳定性优越,即使放置于高温下,动态d33常数的劣化也少。另外,通过形成为包括多晶体的压电陶瓷,与单晶相比,大大抑制加工或输送时的碎屑。进而,通过利用模具等,成形为期望的形状,将其烧成而得到压电陶瓷,因此,还可以作为在烧成后没有形状加工的工序。消除烧成后的形状加工而能够进一步减少碎屑,并且,通过工序的简化,实现低成本化。
进而,在压电陶瓷的两面形成电极,在厚度方向上极化,以厚度纵向的振动模式来工作,由此各向异性大,从而容易得到仅具有压电纵向效果的稳定的输出特性。
附图说明
图1是本发明的压电陶瓷(β=0.44及0.47)和其他压电陶瓷的X射线衍射图。
图2是本发明的压电陶瓷(β=0.44及0.47)和其他压电陶瓷的X射线衍射图,是图1的X射线衍射图的放大图。
图3是作为本发明的压电元件的压力传感器。
图4是说明在本发明中使用的动态d33常数评价装置的说明图。
图5是本发明的压电陶瓷的绝缘电阻率和温度的关系图。
具体实施方式
在本发明的压电陶瓷中,该压电陶瓷以铋层状化合物为主成分,铋层状化合物在将基于摩尔比的组成式表示为Bi4Ti3O12·β[(1-γ)M1TiO3·γM2M3O3]时,满足0.405≤β≤0.498、0≤γ≤0.3,并且,M1为选自Sr、Ba、Ca、(Bi0.5Na0.5)、(Bi0.5Li0.5)及(Bi0.5K0.5)中的至少一种,M2为选自Bi、Na、K及Li中的至少一种,M3为选自Fe及Nb中的至少一种,相对于所述铋层状化合物即主成分100质量份,以氧化物(MnO2、Fe2O3)换算的总量计,含有0.05~1质量份的选自Mn及Fe中的至少一种。
在此,说明将作为系数的β设定为上述范围的理由。在上述组成式中,设定为0.405≤β≤0.498的理由如下:β大于0.498的情况下,200℃下的动态d33常数的温度变化率大于+5%。另外因为:β小于0.405的情况下,200℃下的动态d33常数的温度变化率大于-5%。
这样,在β为0.405≤β≤0.498的范围中的情况下,动态d33常数为比15pC/N充分地大的值,并且,动态d33常数的温度变化率显示从+向-转换的性质。图1是利用X射线衍射解析了改变β时的结晶结构的变化的结果。图2中放大了图1的2θ=32~34°的部分。β=0时,结晶为斜方晶(a轴的长度≠b轴的长度),β=1时,正方晶(a轴的长度=b轴的长度)。在β=0.405~0.495的范围中,正方晶和斜方晶混在,这是组成相边界MPB。该MPB为熟知的PZT压电材料,在PZ的菱面体晶和PT的正方晶以大致1∶1的比例构成的组成区域中形成MPB。在该PZT的MPB附近,d常数显示最大值,压电常数的温度系数大幅度变化。与该现象相同地,0.405≤β≤0.498的组成范围为两种结晶相的边界,因此为显示压电体的特异的现象的组成相边界MPB,动态d33常数的温度变化率减小至约0附近,并且,得到大的动态d33常数。
将基于M2M3O3的置换量γ设为0.1≤γ≤0.3是因为在γ小于0.1的情况下,烧成温度的最佳范围窄到约10℃以内。另外因为:若增加γ,则烧结性变高,动态d33常数不降低,最佳烧成温度范围扩大到约25~30℃,大于0.3的情况下,动态d33常数反而变小。
接着,说明相对于主成分含有的Mn的量。因为:在Mn的含量以MnO2换算时为0.05质量份以下的情况下,由于本材料系为板状结晶,因此,难以烧结,难以得到致密的陶瓷,弹性损失增加,故动态d33常数变得小于15pC/N。另外因为:若大于1质量份,则容易显现烧结性,但容易产生异相,因此,动态d33常数成为15pC/N以下。
另外因为:相对于主成分含有的Fe的量也同样地,Fe的含量在按Fe2O3换算时为0.05质量份以下的情况下,由于本材料系为板状结晶,因此,难以烧结,难以得到致密的陶瓷,弹性损失增加,故动态d33常数变得小于15pC/N。另外因为:若大于1质量份,则容易显现烧结性,但容易产生异相,因此,动态d33常数成为15pC/N以下。
进而,含有Mn和Fe的情况也同样,优选以氧化物(MnO2、Fe2O3)换算的总量计,以0.05~1质量份含有。
重要的是,M2M3O3的M2为选自Bi、Na、K及Li中的至少一种,M3为选自Fe及Nb中的至少一种。进而M2M3O3优选为选自BiFeO3、NaNbO3、KNbO3、LiNbO3中的至少一种。
通过选择这样的化合物,能够得到具有大的动态d33常数,且具有高耐热性,200℃下的动态d33常数的温度变化率小的铋层状结构的非铅压电元件。
本发明的压电陶瓷的组成式表示为Bi4Ti3O12·βM1TiO3(γ=0的情况)、或Bi4Ti3O12·β[(1-γ)M1TiO3·γM2M3O3],作为主结晶相,包括铋层状化合物。即,对于本发明的压电陶瓷而言,在由(Bi2O2)2+(αm-1βmO3m +1)2-书写表示的铋层状结构物的通式中,通过调节α位和β位及氧位上配位的构成元素的种类和量,能够得到具有在m=4的情况下产生的正方晶、和m=3的情况下产生的斜方晶混在的组成相边界MPB的铋层状结构物。其结果,在铋层状化合物中也能够实现PZT中也所知晓的MPB组成附近中的特征性压电特性。
另外,从Mn及Fe选择的至少一种有时固溶于主结晶相中,作为选自一部分Mn及Fe中的至少一种的化合物的结晶,在晶界析出,另外,作为其他结晶相,还有时存在烧绿石相、钙钛矿相、结构不同的铋层状化合物,但微量的情况下,对特性不成为问题。
本发明的压电陶瓷有时从粉碎时的ZrO2球混入Zr等,但微量的情况下,对特性不成为问题。
在本发明的压电陶瓷中,例如,作为原料,可以使用包括SrCO3、BaCO3、CaCO3、Nb2O5、Bi2O3、MnO2、TiO2、Na2CO3、K2CO3、Li2CO3、Fe2O3的各种氧化物或其盐。原料不限定于此,使用通过烧成,生成氧化物的碳酸盐、硝酸盐等金属盐也可。
将这些原料表示为Bi4Ti3O12·β[(1-γ)M1TiO3·γM2M3O3]时,按照相对于满足0.405≤β≤0.498、0≤γ≤0.3的主成分100质量份,以氧化物(MnO2、Fe2O3)换算的总量计,含有0.05~1质量份的选自Mn及Fe中的至少一种的方式进行称量。但是,M1是选自Sr、Ba、Ca、(Bi0.5Na0.5)、(Bi0.5Li0.5)及(Bi0.5K0.5)中的至少一种,M2是选自Bi、Na、K及Li中的至少一种,M3是选自Fe及Nb中的至少一种。对于称量并混合的粉末,按照使平均粒度分布(D50)成为0.5~1μm的范围的方式进行粉碎,在800~1050℃下预烧该混合物,添加规定的有机粘合剂,湿式混合并造粒。利用公知的压制成形等,将这样得到的粉体成形为规定的形状,在大气等氧化性气氛下,在1050~1250℃的温度范围中烧成2~5小时,得到本发明的压电陶瓷。
本发明的压电陶瓷虽然适合作为图3所示的压力传感器用压电陶瓷,但可以使用于除此之外的压电谐振器、超声波振动器、超声波马达及加速度传感器、爆震传感器、AE传感器等压电传感器等中。
图3中示出本发明的压电元件。该压电元件在上述压电陶瓷1的两面形成电极2、3而构成。另外,在厚度方向上实施极化。即,进行基于模拟的应力解析的结果,在作为实际运行下的400N的高加重施加下,在压电元件产生的最大主应力也为陶瓷的机械强度的约1/10以下,因此,在这样的压电元件中,相对于加压力的变化,作为压电陶瓷也稳定,从而能够得到在200℃的高温下也能够使用的非铅的压电元件。
【实施例】
首先,作为起始原料,将纯度99.9%的SrCO3粉末、BaCO3粉末、CaCO3粉末、Bi2O3粉末、TiO2粉末、Na2CO3粉末、K2CO3粉末、Li2CO3粉末、Fe2O3粉末、Nb2O5粉末如下所述地进行称量,即:在将基于摩尔比的组成式表示为Bi4Ti3O12·βM1TiO3(γ=0的情况)、或Bi4Ti3O12·β[(1-γ)M1TiO3·γM2M3O3]时,M1、M2、M3、β、γ成为表1所示的元素、比例。
相对于该主成分100重量份,按照使MnO2粉末及Fe2O3粉末成为表1所示的重量份的方式进行称量并混合,与纯度99.9%的氧化锆球、异丙醇(IPA)一同投入500ml塑料罐(ポリポツト)中,用旋转磨混合16小时。
在大气中干燥混合后的浆料,使其通过#40筛,然后,在大气中95℃下保持3小时而预烧,将该合成粉末与纯度99.9%的ZrO2球和异丙醇(IPA)一同投入500ml塑料罐中,粉碎20小时而得到粉末。
向该粉末中添加适量的有机粘合剂,并造粒,用金属冲压模具以150MPa的负载制作圆柱形状的成形体后,经过脱粘合剂工序,在大气中,在1050~1250℃之间各试料的动态d33常数变得最高的峰温度下,以3小时的条件进行烧成,得到压电元件的尺寸为直径4mm、厚度2mm的圆板状压电陶瓷。另外,对于所述动态d33常数变得最高的烧成峰温度,在-20~+20℃的范围内,以5℃的间隔改变烧成峰温度,进行烧成,制作压电陶瓷。
然后,在圆柱状的压电陶瓷的两面烧接Ag的电极,在200℃的条件下,在厚度方向上施加5kV/mm以上的DC电压,实施极化处理。然后,在300℃下,进行24小时的热老化处理。
然后,使用图4所示的装置,评价动态d33常数。具体来说,首先,向压电元件施加200N的偏压。然后,将施加于压电元件的压力从200N增加至350N后,恢复至200N,反复进行上述动作,用充电来测定从压电元件输出的电荷量的变化。以10Hz的三角波赋予此时的压力变化。还有,利用动态d33常数=输出电荷/压力变化(单位pC/N)的式,求出动态d33常数。同样,求出-40℃及200℃下的动态d33常数的温度变化率。对于动态d33常数的温度变化率例如200℃为止的温度变化率是由室温(25℃)下的动态d33常数和200℃下的动态d33(200℃)常数,利用动态d33常数的温度变化率=(动态d33(200℃)常数-动态d33常数)/动态d33常数的式来求出的。
另外,为了保持200℃的高温下的检测灵敏度,优选压电元件的绝缘电阻为1×109Ω以上。通过使绝缘电阻高于上述值,抑制输出的电荷在压电元件中被消耗的情况,供给于信号处理电路,因此,灵敏度不均少,灵敏度降低或成为噪音源,导致传感器特性的性能变差。
图5中示出试料No.3、5、6及10的绝缘电阻和温度的关系。试料No.3、5及6中,200℃下的绝缘电阻成为1×109Ω以上。相对于此,本发明的范围外的试料No.10在比较低的温度下为1×109Ω以上,但在150℃以上的情况下,比1×109Ω低。
关于各组成,动态d33常数最高的试料的结果示出在表1、2中。
【表1】
*符号表示本发明的范围外的试料
【表2】
*符号表示本发明的范围外的试料
从表1明确可知,在本发明的范围内的试料No.27~30中,动态d33常数得到18.1pC/N以上的高的值,并且,相对于25℃的动态d33常数的-40℃及200℃的动态d33常数的变化率为0.4%以内,从而温度依赖性低。
相对于此,在本发明的范围外的试料No.26中,β高达0.5,因此,动态d33常数低于18pC/N,并且,相对于25℃的动态d33常数的200℃的动态d33常数的变化率大于±5%,温度依赖性高。另外,在本发明的范围外的试料No.31中,β小至0.4,因此,相对于25℃的动态d33常数的200℃的动态d33常数的变化率大于±5%,温度依赖性高。
在本发明的范围内的试料No.4~7、13~19及21~24中,得到动态d33常数15pC/N的高的值,并且,相对于25℃的动态d33常数的-40℃及200℃的动态d33常数的变化率为4.8%以内,从而温度依赖性低。
相对于此,在本发明的范围外的试料No.1~3中,β大于0.5,因此,相对于25℃的动态d33常数的200℃的动态d33常数的变化率大于±5%,温度依赖性高,动态d33常数也随着β的值变大而降低。另外,在本发明的范围外的试料No.8中,β小至0.4,因此,相对于25℃的动态d33常数的200℃的动态d33常数的变化率大于±5%,温度依赖性高。进而,在本发明的范围外的试料No.9~12中,β小于0.25,因此,动态d33常数成为低于15pC/N的值。还有,在本发明的范围外的试料No.20中,相对于25℃的动态d33常数的200℃的动态d33常数的变化率大于±5%,温度依赖性高。在本发明的范围外的试料No.25中,γ高达0.32,因此,相对于25℃的动态d33常数的200℃的动态d33常数的变化率大于±5%,温度依赖性高。
另外,从表2明确可知,在本发明的范围内的试料No.33~38、40、42、43、45~47及49~55中,得到动态d33常数15.1pC/N以上的高的值,并且,相对于25℃的动态d33常数的-40℃及200℃的动态d33常数的变化率为5%以内,从而温度依赖性低。
相对于此,在本发明的范围外的试料No.32、39、44及48中,MnO2或Fe2O3的量多,因此,动态d33常数成为低于15pC/N的值,绝缘电阻也变低。另外,在本发明的范围外的试料No.41中,由于没有作为烧结助剂的MnO2、Fe2O3及M2M3O3,因此烧结不足,不能制作在测定动态d33常数时的加压下不被破坏的试料。
进而,通过比较改变了烧成温度的试料的动态d33常数与动态d33常数最高的试料,调查了动态d33常数的降低幅度在20%以内的烧成温度的范围,将所述范围作为各组成的稳定烧成温度范围。若该温度范围广,则在制造时,即使在烧成温度不均时,动态d33常数的变动也少,能够制作稳定的压电特性的压电陶瓷。
在γ≤0.05的试料No.27~30、40、42、43、45~47及49~55中,稳定烧成温度范围为-5~+5℃的±5℃的范围。相对于此,在0.1≤γ≤0.3的试料No.4~7、13~19、21~24及33~38中为±10℃以上,尤其M2M3O3为BiFeO3的试料No.4~7、13~19、24及33~38中为±15℃以上。
还有,图1及图2中示出试料No.5(β=0.47)和6(β=0.44)的X射线衍射图。从X射线衍射图可知,以铋层状化合物为主结晶相。就试料No.5来说,作为组成式,表示为Bi4Ti3O12·0.47[0.9(Sr0.5Ba0.5)TiO3·0.1BiFeO3]的铋层状化合物、和钙钛矿化合物的组合。另一方面,铋层状化合物作为通式表示为(Bi2O2)2+(αm-1βmO3m+1)2-,但Bi4Ti3O12是通式中的α的元素包括Bi3+,β的元素包括Ti4+的m=3的铋层状化合物,保持电中性条件。
从X射线衍射图确认到,铋层状化合物为主结晶相,因此,认为M2M3O3的钙钛矿化合物取入铋层状化合物的疑似钙钛矿层中,成为了铋层状化合物的一部分。
即,认为:试料No.4的α位包括Bi、Sr、Ba的任一种元素,β位包括Ti、Fe的任一种元素,在α位及β位及氧位具有伴随缺陷的m=4的结晶结构,具体来说,形成了在(Sr0.5Ba0.5)0.4455Bi4Ti3.4455Fe0.0495O13.485中固溶了一部分Mn的铋层状化合物。
这样,认为由m=4构成的铋层状化合物为m=3的铋层状化合物和钙钛矿化合物的复合体,通过将m=4中的钙钛矿化合物的一部分置换为其他钙钛矿化合物,能够得到除了电特性之外,陶瓷强度方面也显示特征性特性的非铅压电材料。
Claims (4)
1.一种压电陶瓷,其特征在于,
所述压电陶瓷以铋层状化合物为主成分,所述铋层状化合物的组成式表示为Bi4Ti3O12·β[(1-γ)M1TiO3·γM2M3O3],满足0.405≤β≤0.498、0≤γ≤0.3,并且,M1为选自Sr、Ba、Ca、Bi0.5Na0.5、Bi0.5Li0.5及Bi0.5K0.5中的至少一种,M2为选自Bi、Na、K及Li中的至少一种,M3为选自Fe及Nb中的至少一种,
相对于所述铋层状化合物即主成分100质量份,以氧化物MnO2、Fe2O3换算的总量计,含有0.05~1质量份的选自Mn及Fe中的至少一种。
2.根据权利要求1所述的压电陶瓷,其特征在于,
0.405≤β≤0.495、0.1≤γ≤0.3。
3.根据权利要求2所述的压电陶瓷,其特征在于,
所述M2M3O3为选自BiFeO3、NaNbO3、KNbO3及LiNbO3中的至少一种。
4.一种压电元件,其特征在于,具备:
权利要求1~3中任一项所述的压电陶瓷;和
分别在该压电陶瓷的两面形成的电极。
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